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Licensed Unlicensed Requires Authentication Published by De Gruyter July 2, 2018

Redox-induced nucleation and growth of goethite on synthetic hematite nanoparticles

  • Jeanette L. Voelz , William A. Arnold and R. Lee Penn EMAIL logo
From the journal American Mineralogist


The iron (oxyhydr)oxides hematite (α-Fe2O3) and goethite (α-FeOOH) are natural and reactive minerals common in soils and sediments, and their adsorption of Fe(II) produces reactive surface sites that facilitate reduction of oxidized environmental pollutants. Single-exposure experiments with 4-chloronitrobenzene showed that hematite is more reactive than goethite, when normalized by surface area loading. Interestingly, the product of Fe(II) oxidation is a mixture of goethite and hematite, and the goethite to hematite ratio depends on the distribution of Fe(II) activated surface sites, which is a function of aqueous Fe(II) concentration, surface area loading, and pH. More goethite is produced under conditions of higher Fe(II), lower surface area loading, and higher pH. Recurrent-exposure experiments showed a substantial decrease in reaction rate after one to three exposures, a trend suggestive of reaction contributions from the increasing goethite surface area over time. Using known atomic surface geometry for goethite and hematite, the hematite {012} facet is proposed as the site of primary mineral growth with goethite {021} at the interface between the two minerals. These results have implications in contaminant fate modeling, where the mineral phases present in the environment, the minerals likely to form, and the surrounding aqueous conditions all have an impact on contaminant reaction rate.


This work was funded by the NSF grant ECS-1012193 and CHE-1507496. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. Thanks to Thomas E. Webber, who performed the BET measurements.

References cited

Barron, V., and Torrent, J. (1996) Surface hydroxyl configuration of various crystal faces of hematite and goethite. Journal of Colloid and Interface Science, 177, 407–410.10.1006/jcis.1996.0051Search in Google Scholar

Boparai, H.K., Comfort, S.D., Shea, P.J., and Szecsody, J.E. (2008) Remediating explosive-contaminated groundwater by in situ redox manipulation (ISRM) of aquifer sediments. Chemosphere, 71, 933–941.10.1016/j.chemosphere.2007.11.001Search in Google Scholar PubMed

Catalano, J.G., Fenter, P., Park, C., Zhang, Z., and Rosso, K.M. (2010) Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH. Geochimica et Cosmochimica Acta, 74, 1498–1512.10.1016/j.gca.2009.12.018Search in Google Scholar

Chopard, A., Benzaazoua, M., Bouzahzah, H., Plante, B., and Marion, P. (2017) A contribution to improve the calculation of the acid generating potential of mining wastes. Chemosphere, 175, 97–107.10.1016/j.chemosphere.2017.02.036Search in Google Scholar PubMed

Chun, C.L., Penn, R.L., and Arnold, W.A. (2006) Kinetic and microscopic studies of reductive transformations of organic contaminants on goethite. Environmental Science and Technology, 40, 3299–3304.10.1021/es0600983Search in Google Scholar PubMed

Cornell, R.M., and Schwertmann, U. (1996) The Iron Oxides, 360 p. Wiley-VCH, Weinheim, Germany.Search in Google Scholar

Dunnivant, F.M., Schwarzenbach, R.P., and Macalady, D.L. (1992) Reduction of substituted nitrobenzenes in aqueous solutions containing natural organic matter. Environmental Science and Technology, 26, 2133–2141.10.1021/es00035a010Search in Google Scholar

Elsner, M., Haderlein, S.B., Kellerhals, T., Luzi, S., Zwank, L., Angst, W., and Schwarzenbach, R.P. (2004a) Mechanisms and products of surface-mediated reductive dehalogenation of carbon tetrachloride by Fe(II) on goethite. Environmental Science and Technology, 38, 2058–2066.10.1021/es034741mSearch in Google Scholar PubMed

Elsner, M., Schwarzenbach, R.P., and Haderlein, S.B. (2004b) Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants. Environmental Science and Technology, 38, 799–807.10.1021/es0345569Search in Google Scholar PubMed

Faivre, D. (2016) Introduction. In D. Faivre, Ed., Iron Oxides: From Nature to Applications, p. 1–5. Wiley.10.1002/9783527691395Search in Google Scholar

Guo, H., and Barnard, A.S. (2011) Thermodynamic modelling of nanomorphologies of hematite and goethite. Journal of Materials Chemistry, 21, 11,566.10.1039/c1jm10381dSearch in Google Scholar

Hofstetter, T.B., Heijman, C.G., Haderlein, S.B., Holliger, C., and Schwarzenbach, R.P. (1999) Complete reduction of TNT and other (poly)nitroaromatic compounds under iron-reducing subsurface conditions. Environmental Science and Technology, 33, 1479–1487.10.1021/es9809760Search in Google Scholar

Howard, P.H., and Muir, D.C.G. (2013) Identifying new persistent and bioaccumulative organics among chemicals in commerce. III: Byproducts, impurities, and transformation products. Environmental Science and Technology, 47, 5259–5266.10.1021/es4004075Search in Google Scholar

Jeon, B.H., Dempsey, B.A., Burgos, W.D., and Royer, R.A. (2001) Reactions of ferrous iron with hematite. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 191, 41–55.10.1016/S0927-7757(01)00762-2Search in Google Scholar

Jeon, B.H., Dempsey, B.A., and Burgos, W.D. (2003) Kinetics and mechanisms for reactions of Fe(II) with iron(III) oxides. Environmental Science and Technology, 37, 3309–3315.10.1021/es025900pSearch in Google Scholar PubMed

Ju, K.-S., and Parales, R.E. (2010) Nitroaromatic compounds, from synthesis to biodegradation. Microbiology and Molecular Biology Reviews, 74, 250–272.10.1128/MMBR.00006-10Search in Google Scholar PubMed PubMed Central

Klausen, J., Troeber, S.P., Haderlein, S.B., and Schwarzenback, R.P. (1995) Reduction of substituted nitrobenzenes by Fe(II) in aqueous mineral suspensions. Environmental Science and Technology, 29, 2396–2404.10.1021/es00009a036Search in Google Scholar PubMed

Lagroix, F., Banerjee, S.K., and Jackson, M.J. (2016) Geological occurrences and relevance of iron oxides. In Iron Oxides: From Nature to Applications, p. 7–30, Wiley.10.1002/9783527691395.ch2Search in Google Scholar

Larese-Casanova, P., and Scherer, M.M. (2007) Fe(II) sorption on hematite: New insights based on spectroscopic measurements. Environmental Science and Technology, 41, 471–477.10.1021/es0617035Search in Google Scholar PubMed

Larese-Casanova, P., Kappler, A., and Haderlein, S.B. (2012) Heterogeneous oxidation of Fe(II) on iron oxides in aqueous systems: Identification and controls of Fe(III) product formation. Geochimica et Cosmochimica Acta, 91, 171–186.10.1016/j.gca.2012.05.031Search in Google Scholar

Maqueda, C., Undabeytia, T., Villaverde, J., and Morillo, E. (2017) Behaviour of glyphosate in a reservoir and the surrounding agricultural soils. Science of the Total Environment, 593– 594, 787–795.10.1016/j.scitotenv.2017.03.202Search in Google Scholar PubMed

Navrotsky, A., Mazeina, L., and Majzlan, J. (2008) Size-driven structural and thermodynamic complexity in iron oxides. Science, 319, 1635–1638.10.1126/science.1148614Search in Google Scholar PubMed

Pauling, L., and Hendricks, S.B. (1925) The crystal structures of hematite and corundum. Journal of the American Ceramic Society, 47, 781–790.10.1021/ja01680a027Search in Google Scholar

Pecher, K., Haderlein, S.B., and Schwarzenbach, R.P. (2002) Reduction of poly-halogenated methanes by surface-bound Fe(II) in aqueous suspensions of iron oxides. Environmental Science and Technology, 36, 1734–1741.10.1021/es011191oSearch in Google Scholar PubMed

Pedersen, H.D., Postma, D., Jakobsen, R., and Larsen, O. (2005) Fast transformation of iron oxyhydroxides by the catalytic action of aqueous Fe(II). Geochimica et Cosmochimica Acta, 69, 3967–3977.10.1016/j.gca.2005.03.016Search in Google Scholar

Penn, R.L., Erbs, J.J., and Gulliver, D.M. (2006) Controlled growth of alpha-FeOOH nanorods by exploiting-oriented aggregation. Journal of Crystal Growth, 293, 1–4.10.1016/j.jcrysgro.2006.05.005Search in Google Scholar

Rosso, K.M., Smith, D.M.A., and Dupuis, M. (2003) An ab initio model of electron transport in hematite (α-Fe2O3) basal planes. Journal of Chemical Physics, 118, 6455–6466.10.1063/1.1558534Search in Google Scholar

Rosso, K.M., Yanina, S.V., Gorski, C.A., Larese-Casanova, P., and Scherer, M.M. (2010) Connecting observations of hematite (α-Fe2O3) growth catalyzed by Fe(II). Environmental Science and Technology, 44, 61–67.10.1021/es901882aSearch in Google Scholar PubMed

Scherer, M.M., Richter, S., Valentine, R.L., and Alvarez, P.J.J. (2000) Chemistry and microbiology of permeable reactive barriers for in situ groundwater clean up. Critical Reviews in Environmental Science and Technology, 30, 363–411.10.1080/10643380091184219Search in Google Scholar

Schwertmann, U., and Murad, E. (1983) Effect of pH on the formation of goethite and hematite from ferrihydrite. Clays and Clay Minerals, 31, 277–284.10.1346/CCMN.1983.0310405Search in Google Scholar

Stemig, A.M., Do, T.A., Yuwono, V.M., Arnold, W.A., and Penn, R.L. (2014) Goethite nanoparticle aggregation: Effects of buffers, metal ions, and 4-chloronitrobenzene reduction. Environmental Science: Nano, 1, 478–487.10.1039/C3EN00063JSearch in Google Scholar

Strehlau, J.H., Stemig, M.S., Penn, R.L., and Arnold, W.A. (2016) Facet-dependent oxidative goethite growth as a function of aqueous solution conditions. Environmental Science and Technology, 50, 10,406–10,412.10.1021/acs.est.6b02436Search in Google Scholar

Strehlau, J.H., Schultz, J.D., Vindedahl, A.M., Arnold, W.A., and Penn, R.L. (2017) Effect of nonreactive kaolinite on 4-chloronitrobenzene reduction by Fe(II) in goethite–kaolinite heterogeneous suspensions. Environmental Science: Nano, 4, 325–334.10.1039/C6EN00469ESearch in Google Scholar

Szytula, A., Bureqicz, A., Dimitrijevic, Z., Krasnicki, S., Rzany, H., Todorovic, J., Wanic, A., and Wolski, W. (1968) Neutron diffraction studies of α-FeOOH. Physica Status Solidi, 26, 429–434.10.1515/9783112496763-004Search in Google Scholar

Tanwar, K.S., Petitto, S.C., Ghose, S.K., Eng, P.J., and Trainor, T.P. (2008) Structural study of Fe(II) adsorption on hematite(1102). Geochimica et Cosmochimica Acta, 72, 3311–3325.10.1016/j.gca.2008.04.020Search in Google Scholar

Valencia-Avellan, M., Slack, R., Stockdale, A., and Mortimer, R.J.G. (2017) Understanding the mobilisation of metal pollution associated with historical mining in a carboniferous upland catchment. Environmental Science: Processes Impacts, 19, 1061–1074.10.1039/C7EM00171ASearch in Google Scholar

Vindedahl, A.M., Arnold, W.A., and Penn, R.L. (2015) Impact of Pahokee Peat humic acid and buffer identity on goethite aggregation and reactivity. Environmental Science: Nano, 2, 509–517.10.1039/C5EN00141BSearch in Google Scholar

Wehrli, B., Sulzberger, B., and Stumm, W. (1989) Redox processes catalyzed by hydrous oxide surfaces. Chemical Geology, 78, 167–179.10.1016/0009-2541(89)90056-9Search in Google Scholar

West, A.R. (2014) Solid State Chemistry and its Applications, p. 248–258. Wiley, U.K.Search in Google Scholar

Williams, A.G.B., and Scherer, M.M. (2004) Spectroscopic evidence for Fe(II)-Fe(III) electron fransfer at the iron oxide-water interface. Environmental Science and Technology, 38, 4782–4790.10.1021/es049373gSearch in Google Scholar PubMed

Yang, H., Lu, R., Downs, R.T., and Costin, G. (2006) Goethite, α-FeO(OH), from single-crystal data. Acta Crystallographica, E62, i250–i252.10.1107/S1600536806047258Search in Google Scholar

Received: 2017-10-18
Accepted: 2018-03-27
Published Online: 2018-07-02
Published in Print: 2018-07-26

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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